Three-component alkyl aluminum halide catalysts for olefin polymerization



United States Patent 3,213,073 THREE-COMPONENT ALKYL ALUMINUM HALIDE CATALYSTS FOR OLEFIN POLYMERIZATION Harry W. Coover, Jr., and Frederick B. Joyner, Kingsport,

TemL, assignors to Eastman Kodak Company, Rochester, N .Y., a corporation of New Jersey No Drawing. Filed Dec. 23, 1960, Ser. No. 77,837 The portion of the term of the patent subsequent to Sept. 1, 1981, has been disclaimed and dedicated to the Public 18 Claims. (Cl. 26093.7)

This application is a continuation-in-part of our copending application Serial No. 724,909, filed March 31, 1958, and now US. Patent 2,969,345.

This invention relates to a new and improved polym erization process and is particularly concerned with the use of a novel catalyst combination for preparing high molecular weight solid polyolefins, such as polypropylene, of high density and crystallinity. In a particular aspect the invention is concerned with the preparation of polypropylene and higher polyolefins using a particular catalyst combination which has unexpected catalytic activity, and which gives products characterized by unusually high crystallinity, softening point, thermal stability, stiffness and being substantially free of non-crystalline polymers.

Polyethylene has heretofore been prepared by high pressure processes to give relatively flexible polymers having a rather high degree of chain branching and a density considerably lower than the theoretical density. Thus, pressures of the order of 500 atmospheres or more and usually of the order of 1000 to 1500 atmospheres are commonly employed. It has been found that more dense polyethylenes can be produced by certain catalyst combinations to give polymers which have very little chain branching and a high degree of crystallinity. The exact reason Why certain catalyst combinations give these highly dense and highly crystalline polymers is not readily understood. Furthermore, the activity of the catalysts ordinarily depends upon certain specific catalyst combinations and the results are ordinarily highly unpredictable,

' since relatively minor changes in the catalyst combination often lead to liquid polymers rather than the desired solid polymer.

Certain of the trialkyl aluminum compounds have been used in conjunction with inorganic halides to give high molecular weight polyethylene. Thus, triethylaluminum in conjunction with titanium tetrachloride permits a low temperature, low pressure polymerization of ethylene to highly crystalline product. When this catalyst mixture is employed to polymerize propylene, the product is predominantly polymeric oils and rubbers with a comparatively small amount of high molecular weight crystalline products. Furthermore, a mixture of ethyl aluminum dihalide and titanium trihalide is ineffective as a polymerization catalyst, for example, for polymerizing propylene.

Some of the catalysts that are effective for producing crystalline high density polyethylene cannot be used to produce a similar type of polypropylene. Thus, one cannot predict whether a specific catalyst combination will be effective to produce crystalline high density polymers with specific a-olefins.

This invention is concerned with and has for an object the provision of improved processes whereby a-monoolefins and particularly propylene can be readily polymerized by catalytic means to give high molecular weight, highly crystalline polymers. A particular object of the invention is to provide a catalyst combination which has unexpected catalytic activity for the polymerization of Otmonoolefins to form crystalline high density polymers. Other objects will be apparent from the description and claims which follow.

3,213,073 Patented Oct. 19, 1965 The above and other objects are attained by means of this invention, wherein u-monoolefins, either singly or in admixture, are readily polymerized to high molecular weight solid polymers by effecting the polymerization in the presence of a catalytic mixture containing an aluminum dihalide having the formula R AlX wherein R is a hydrocarbon radical containing 1 to 12 carbon atoms and selected from the group consisting of alkyl, aryl and aralkyl and X is a halide selected from the group consisting of chlorine, bromine and iodine, a compound of a transition metal selected from the group consisting of titanium, zirconium, vanadium, chromium and molybdenum, said compound being selected from the group consisting of halides, alkoxyhalides and acetylacetonates, and an amide third component. The amide can have the structural formula I R1N wherein R is a radical selected from the group consisting of hydrogen, alkyl radicals containing from 1 to 20 carbon atoms, phenyl, carboxyl, OR, -N(R) wherein R is a radical containing 1 to 4 carbon atoms and u (CH2)nCN wherein n is an integer of 1 to 4, and each of R and R is a radical selected from the group consisting of hydrogen, alkyl radicals containing 1 to 8 carbon atoms, phenyl and cyclohexyl.

The amide third component of the catalyst can have the structural formulas wherein n is an integer of 1 to 4 and R is a radical selected from the group consisting of alkyl radicals containing 1 to 4 carbon atoms and phenyl.

Other third components that can be employed in the catalyst are phosphorus-containing amides having the structural formulas:

5 6)x( 7)y and it roman) x (011m wherein x and y are whole numbers from 1 to 3 and 0 to 2 respectively, the sum of x and y being 3, and x and y are whole numbers from 1 to 2, the sum of x and y being 3, and R R and R are alkyl radicals containing 1 to 8 carbon atoms.

Amide third components that can be used in the catalyst system are N,N-dimethylformamide, N,N-dimethylacetamide, N,N diethylacetamide, N cyclohexylacetamide,

N t butylbenzamide, N methyl N phenylacetamide,

zoylmorpholine, N,N' diacetylpiperazine, n butyloxamate, ethyloxanilate, ethyl carbonate, diethyl N-dimethylamidophosphate, ethyl N,N tetraethylamidophosphate, diethyl N dimethylamidophosphite, ethyl N,N- tetraethyl diamidophosphite, N,N,N-hexaethyl triamidophosphite, dibutyl N dipropyl amidophosphate, npentyl N,N tetrabutyl amidophosphate, diproply N dioctyl amidophosphite, n hexyl N,N tetrabutyl diamidophosphite, N,N,N hexa(n hexyl)triamidophosphite.

Catalyst mixtures that can be employed in practicing our invention are:

(a) Ethyl aluminum dichloride, titanium trichloride and n-cyclohexylacetamide.

(b) Ethyl aluminum dibromide, dibutoxy titanium dichloride and N-methyl-N-phenylacetamide.

(c) Phenyl aluminum dichloride, zirconium acetylacetonate and palrnitamide.

(d) Butyl aluminum diiodide, zirconium tetrachloride and acetanilide.

(e) Cyclohexyl aluminum dichloride, vanadium trichloride and isobutyramide.

(f) Tolyl aluminum dichloride, molybdenum pentachloride and N,N-di-t-butylurea.

(g) Ethyl aluminum dichloride, titanium tetrachloride and ethyl carbamate.

(h) Octyl aluminum dibromide, titanium trichloride and ethyl N,N-tetraethyl amidophosphate.

(i) Methyl aluminum diiodide, vanadium trichloride and dimethyl N-dimethyl amidophosphate.

(j) Octyl aluminum dichloride, titanium trichloride and N,N,N-hexamethyl triamidophosphite.

(k) Ethyl aluminum dichloride, titanium tetrachloride and dimethyl N-dimethylamidophosphite.

The catalytic activity of this mixture was wholly unexpected, particularly since the alkyl aluminum dihalides either singly or in admixture with the aforementioned metal compounds are ineifective as polymerization catalysts. Also, the third component of this catalyst composition is not an effective polymerization catalyst. The inventive process is carried out in liquid phase in an inert organic liquid and preferably an inert liquid hydrocarbon vehicle, but the process can be carried out in the absence of inert diluent. The process proceeds with excellent results over a temperature range of from C. to 250 C., although it is preferred to operate within the range of from about 50 C. to about 150 C. Likewise, the reaction pressures may be varied widely from about atmospheric pressure to vary high pressures of the order of 20,- 000 psi. or higher. A particular advantage of the invention is that pressures of the order of 30 to 1000 psi. give excellent results, and it is not necessary to employ the extremely high pressures which were necessary heretofore. The liquid vehicle employed is desirably one which serves both as a liquid reaction medium and as a solvent for the solid polymerization products at the temperature of polymerization.

The invention is of particular importance in the preparation of highly crystalline polyethylene, polypropylene, the polybutenes and polystyrene although it can be used for polymerizing mixtures of ethylene and propylene as well as other a-monoolefins containing up to carbon atoms. The polyethylene which is obtained in accordance with this invention has a softening or fusion point greater than 120 C. whereby the products prepared therefrom can be readily employed in contact with boiling water without deformation or other deleterious effects. The process of the invention readily results in solid polymers having molecular weights greater than 1000 and usually greater than 10,000. Furthermore, polymers having molecular weights of as much as 1,000,000 or higher can be readily prepared if desired. The high molecular weight, high density polyethylenes of this invention are insoluble in solvents at ordinary temperatures but they are soluble in such solvents as xylene, toluene or tetralin at temperatures above 100 C. These solubility characteristics make it possible to carry out the polymerization process under conditions wherein the polymer formed is soluble in the reaction medium during the polymerization and can be precipitated therefrom by lowering the temperature of the resulting mixture.

The polyethylenes of this invention are highly crystalline and usually exhibit crystallinity above as shown by X-ray diagrams. Ordinarily, the crystallinities of the polyethylenes obtained by this process average close to In contrast to the high pressure polyethylene known heretofore, the number of methyl groups per hundred carbon atoms in the polyethylenes of this invention is of the order of 0.5 or lower. The densities are of the order of 0.945 or higher, with densities of the order of 0.96 or higher being obtained in many cases. The inherent viscosity as measured in tetralin at C. can be varied from about 0.5 or lower to 5.0 or higher. Melt indices as measured by the standard ASTM method may be varied from about 0.1 to 100 or even higher.

The novel catalysts described above are particularly useful for polymerizing propylene to form a crystalline, high density polymer. The polypropylene produced has a softening point above 155 C. and a density of 0.91 and higher. Usually, the density of the polypropylene is of the order of 0.91 to 0.92.

The polyolefins prepared in accordance with the invention can be molded or extruded and can be used to form plates, sheets, films or a variety of molded objects which exhibit a higher degree of stiffness than do the corresponding high pressure polyolefins. The products can be extruded in the form of pipe or tubing of excellent rigidity and can be inject-ion molded intoa great variety of articles. The polymers can also be cold drawn into ribbons, bands, fibers or filaments of high elasticity and rigidity. Fibers of high strength can be spun from the molten polyolefins obtained according to this process.

As has been indicated above, the improved results obtained in accordance with this invention depend upon the particular catalyst combination. Thus, one of the components of the catalyst is a compound of aluminum dihalide having the formula R AlX wherein R is a hydrocarbon radical containing 1 to 12 carbon atoms and selected from the group consisting of alkyl, aryl and aralkyl. Among these hydrocarbon radicals are methyl, ethyl, propyl, butyl, phenyl, phenylethyl, naphthyl and the like, and the halogen selected from the group consisting of chlorine, bromine and iodine. The preferred alkyl aluminum dihalides are the lower alkyl derivatives, and the most preferred is ethyl aluminum dichloride. Another component of the catalyst composition is a compound of a transition metal selected from the group consisting of titanium, zirconium, vanadium, chromium and molybdenum. In these compounds the transition metal can be at its maximum valence, but it is possible to employ a compound of a transition metal having a reduced valence. Among the transition metal compounds that can be used are the halides, alkoxyhalides and acetylacetonates of the above-named transition metals. Such compounds as titanium tetrachloride, titanium trichloride, dibutoxy titanium dichloride, diethoxy titanium dichloride and titanium acetylacetonate can be used in the catalyst combination. Similar compounds of z-ironium, vanadium, chromium and molybdenum can also be used. For the most desirable results it is preferred to use a halide of titanium having either its maximum valency or a reduced valency, and specifically it is preferred to employ either titanium tetrachloride or titanium trichloride in the catalyst composition. The third component of the catalyst composition is an amide as previously described.

The limiting factor in the temperature of the process appears to be the decomposition temperature of the catalyst. Ordinarily, temperatures from 50 C. to C. are employed, although temperatures as low as 0 C. or as high as 250 C. can be employed if desired. Usually, it is not desirable or economical to efiect the polymerization at temperatures below C. and the process can be readily controlled at room temperature or higher which is an advantage from the standpoint of commercial processing. The pressure employed is usually only suflicient to maintain the reaction mixture in liquid form during the polymerization, although higher pressures can be used if desired. The pressure is ordinarily achieved by pressuring the system with the monomer whereby additional monomer dissolves in the reaction vehicle as the polymerization progresses.

The polymerization embodying the invention can be carried out batchwise or in a continuous flowing stream process. The continuous processes are preferred for economic reasons, and particularly good results are obtained using continuous processes wherein a polymerization mixture of constant composition is continuously and progressively introduced into the polymerization zone and the mixture resulting from the polymerization is continuously and progressively withdrawn from the polymen'zation zone at an equivalent rate, whereby the'relative concentration of the various components in the polymerization zone remains substantially unchanged during the process. This results in formation of polymers of extremely uniform molecular weight distribution over a relatively narrow range. Such uniform polymers possess distinct advantages since they do not contain any substantial amount of the low molecular weight or high molecular weight formations which are ordinarily found in polymers prepared by batch reactions.

In a continuous flowing stream process, the temperature is desirably maintained at a substantially constant value with-in the preferred range in order to achieve the highest degree of uniformity. Since it is desirable to employ a solution of the monomer of relatively high concentration, the process is desirably effected under a pressure of from 30 to 1000 psi. obtained by pressuring the system with the monomer being polymerized. The amount of vehicle employed can be varied over rather wide limits with relation to the monomer and catalyst mixture. Best results are obtained using a concentration of catalyst of from about 0.1% to about 2% by weight based on the Weight of the vehicle. The concentration of the monomer in the vehicle will vary rather widely depending upon the reaction conditions and will usually range from about 2 to 50% by weight. For a solution type of process it is preferred to use a concentration from about 2 to about 10% by weight based on the weight of the vehicle, and for a slurry type of process higher concentrations, for example up to 40% and higher are preferred. Higher concentrations of monomer ordinarily increase the rate of polymerization, but concentrations above 5 to by weight in a solution process are ordinarily less desirable because the polymer dissolved in the reaction medium results in a very viscous solution.

The preferred molar ratio of aluminum compound to transition metal compound can be varied within the range of 1:05 to 1:2, and the molar ratio of aluminum compound to the third component of the catalytic mixture can be varied within the range of 1:1 to 120.25, but it will be understood that higher and lower molar ratios are within the scope of this invention. A particularly effective catalyst contains one mole of transition metal compound and 0.5 mole of the third component per mole of aluminum dihalide. The polymerization time can be varied as desired and will usually be of the order of from 30 minutes to several hours in batch processess. Contact times of from 1 to 4 hours are commonly employed in autoclave type reactions. When a continuous process is employed, the contact time in the polymerization zone can also be regulated as desired, and in some cases it is not necessary to employ reaction or contact times much beyond one-half to one hour since a cyclic system can be employed by precipitation of the polymer and return of the vehicle and unused catalyst to the charging zone wherein the catalyst can be replenished and additional monomer introduced.

The organic vehicle employed can be an aliphatic a1- kane or cycloalkane such as pentane, hexane, heptane or cyclohexane, or a hydrogenated aromatic compound such as tetrahydronaphthalene or decahydronaphthalene, or a high molecular Weight liquid paraflin or mixture of paraflins which are liquid at the reaction temperature, or an aromatic hydrocarbon such as benzene, toluene, xylene, or the like, or a halogenated aromatic compound such as chlorobenzene, chloronaphthalene, or orthdichlorobenzene. The nature of the vehicle is subject to considerable variation, although the vehicle employed should be liquid under the conditions of reaction and relatively inert. The hydrocarbon liquids are desirably employed. Other solvents which can be used include ethyl benzene, isopropyl benzene, ethyl toluene, n-propyl benzene, diethyl benzenes, mono and dialkyl naphthalenes, n-pentane, n-octane, isooctane, methyl cyclohexane, tetralin, decalin, and any of the other well known inert liquid hydrocarbons. The diluents employed in practicing this invention can be advantageously purified prior to use in the polymerization reaction by contacting the diluent, for example, in a distillation procedure or otherwise, with the polymerization catalyst to remove undesirable trace impurities. Also, prior to such purification of the diluent the catalyst can be contacted advantageously with a polymerizable a-monoolefin.

The polymerization ordinarily is accomplished by merely admixing the components of the polymerization mixture, and no additional heat is necessary unless it is desired to effect the polymerization at an elevated temperature in order to increase the solubility of polymeric product in the vehicle. When the highly uniform polymers are desired employing the continuous process wherein the relative proportions of the various components are maintained substantially constant, the temperature is desirably controlled within a relatively narrow range. This is readily accomplished since the solvent vehicle forms a high percentage of the polymerization mixture and hence can be heated or cooled to maintain the temperature as desired.

A particularly effective catalyst for polymerizing ethylene, propylene, styrene and other a-monoolefins in accordance with this invention is a mixture of ethyl aluminum dichloride, titanium trichloride and N,N-dimethylformamide. The importance of the various components of this reaction mixture is evident from the fact that a mixture of ethyl aluminum dichloride and titanium trichloride is inelfective for polymerizing propylene. However, when the above formamide or other third component within the scope of this invention is added to the mixture the resulting catalyst composition is highly effective for polymerizing propylene to form a highly crystalline, high-density, high-softening polymer.

The invention is illustrated by the following examples of certain preferred embodiments thereof.

Example 1 Inside a nitrogen-filled dry box the following materials were placed into a dry 500-ml. pressure bottle: ml. of dry heptane and 2 g. of catalyst mixture which comprised a 2: 1:3 molar ratio respectively of ethylaluminum dichloride, N,N-dimethylformamide, and titanium trichloride. The pressure bottle was removed from the dry box and attached to a Parr hydrogenation apparatus in which propylene had been admitted to the reservoir in place of hydrogen. Shaking was initiated and the pressure bottle and its contents were heated to 75 C. under 30 psi. propylene pressure and maintained under these conditions for a total of 6 hours. The reaction mixture was detached from the shaking apparatus and dry methanol was added to destroy the catalyst. After several washes with hot, dry methanol a total of 11 g. of highly crystalline polypropylene was obtained from this reaction mixture. The inherent viscosity of the polypropylene was 3.8. When a control run was carried out using ethylaluminum dichloride and titanium trichloride with no N,N-dimethylformamide present, a total of 2 g. of catalyst mixture gave no solid polypropylene under the above conditions.

Example 2 Inside a nitrogen-filled dry box, the following materials were placed into a 285 ml. stainless steel autoclave: 100 ml. of dried mineral spirits (B.P. 197 C.), a total of 1 g. of a 2:1:3 molar ratio of ethylaluminum dichloride, N,N-dimethylacetamide, and titanium trichloride. This autoclave was then placed in a rocker attached to a source of dry liquid propylene and 100 ml. of dry propylene monomer was added. Rocking was initiated, and the mixture was heated to 85 C. and maintained there for a period of 4 hours. The polymer was worked up as described in Example 1, a yield of 39.0 g. being obtained having ,an inherent viscosity of 4.0. When hydrogen was admitted to the polymerization zone and maintained there during the polymerization period at a pressure of 50 p.s.i., the inherent viscosity of the polypropylene obtained was 2.5. Upon increasing the hydrogen pressure to 500 p.s.i. the inherent viscosity of the polypropylene obtained was 0.40.

Example 3 The procedure of Example 2 Was used to polymerize 1- butene using 1 g. of catalyst comprising a 2:1:2 molar ratio respectively of ethylaluminum dibromide, N-t-butylbenzamide, and titanium trichloride. A 38.5 g. yield of highly crystalline poly-l-bu-tene was obtained.

Example 4 The procedure of Example 2 was employed to polymerize 3-methyl-1-butene using 1 g. of total catalyst comprising a 2:05 :3 molar ratio of ethylaluminum dichloride, N-benzylacetamide, and vanadium trichloride. A 35.8 g. yield of highly crystalline poly(3-methyl-1-butene) was obtained. 1

Example 5 The procedure of Example 2 was employed to polymerize styrene using 1 g. of catalyst comprising a 1:1:3 molar ratio of ethylalumi-num dibromide, n-heptamide, and vanadium trichloride. A 24.0 g. yield of highly crystalline polystyrene was obtained.

Example 6 The procedure of Example 2 was employed to polymerize allylbenzene using 2 g. of catalyst comprising a 2: 1 :3 molar ratio of cyclohexylaluminum dichloride, N,N-di-tbutylurea, and zirconium tetrachloride. A good yield of highly crystalline poly(allylbenzene) was obtained.

Example 7 The procedure of Example 2 was employed to polymerize vinylcyclohexane using 1 g. of catalyst comprising a 1:1:1 molar ratio of phenylaluminum dichloride, N,N,- N,N'-tetramethyladipamide, and molybdenum pentachloride. A 36.0 g. yield of highly crystalline poly(vinylcyclohexane) of inherent viscosity 2.7 was obtained.

Example 8 The procedure of Example 2 was employed to polymerize butadiene using 1 g. of catalyst comprising a 2: 1:3 molar ratio of tolyl aluminum dichloride, n-butyl oxamate and titanium tetrabutoxide. A 20 g. yield ofpolybutadiene of inherent viscosity 1.8 was obtained.

Example 9 The procedure of Example 2 was followed except that the catalyst charge was 1 g. of a mixture of ethylaluminum dichloride, titanium trichloride and N-N-diethylacetamide in a molar ratio of 121:0.5. No solvent was employed and the polymerization temperature was 85 C.

o 0 The crystalline polypropylene obtained had a density of 0.915 and an inherent viscosity of 2.85. Other amides which may be used in place of N,N-diethylacetamide to give similar results are N-cyclohexylacetamide, N-methyl- N-phenylacetamide, palrnitamide, stearanilide, acetanilide, isobutyramide, tetramethylurea, succinimide, N- methylisobutyramide, N-benzoylmorpholine, N,N'-diacetylpiperazine, ethyl oxanilate, ethyl carbamate, and the like.

Thus, by means of this invention polyolefins such as polyethylene and polypropylene are readily produced using a catalyst combination which, based on the knowledge of the art, would not be expected to be effective. The polymers thus obtained can be extruded, mechanically milled, cast or molded as desired. The polymers can be used as blending agents with the relatively more flexible high pressure polyethylenes to give any desired combination of properties. The polymers can also be blended with antioxidants, stabilizers, plasticizers, fillers, pigments and the like, or mixed with other polymeric materials, waxes and the like. In general, .aside from the relatively higher values for such properties as softening point, density, stiffness and the like, the polymers embodying this invention can be treated in similar manner to those obtained by other processes.

From the detailed disclosure of this invention it is quite apparent that in this polymerization procedure a novel catalyst not suggested in prior art polymerization procedures is employed. As a result of the use of this novel catalyst it is possible to produce polymeric hydrocarbons, particularly polypropylene, having properties not heretofore obtainable. For example, polypropylene prepared in the presence of catalyst combinations Within the scope of this invention is substantially free of rubbery and oily polymers and thus it is not necessary to subject such polypropylene of this invention to extraction procedures in order to obtain a commercial product. Also, polypropylene produced in accordance with this invention possesses unexpectedly high crystallinity, an unusual-1y high softening point and outstanding thermal stability. Such polypropylene also has a very high stiffness as a result of the unexpectedly high crystallinity. The properties imparted to polypropylene prepared in accordance with this invention thus characterize and distinguish this polypropylene from polymers prepared by prior art polymerization procedures.

The novel catalysts defined above can be used to produce high molecular weight crystalline polymeric hydrocarbons. The molecular Weight of the polymers can be varied over a wide range by introducing hydrogen to the polymerization reaction. Such hydrogen can be introduced separately or in admixture With the olefin monomer. The polymers produced in accordance with this invention can be separated from polymerization catalyst by suitable extraction procedures, for example, by washing with water or lower aliphatic alcohols such as methanol.

The catalyst compositions have been described above as being efiective primarily for the polymerization of amonoolefins. These catalyst compositions can, however, be used for polymerizing other a-olefins, and it is not necessary to limit the process of the invention to monoolefins. Other a-olefins that can be used are butadiene, isoprene, 1,3-pentadiene and the like.

Although the invention has been described in considerable detail with reference to certain preferred embodiments thereof, variations and modifications can be eifected Within the spirit and scope of this invention as described herein-above and as defined in the appended claims.

We claim:

1. In the polymerization of an olefinic hydrocarbon material containing at least three carbon atoms to form solid crystalline polymer, the improvement which comprises catalyzing the polymerization with a catalytic mixture consisting essentially of .an aluminum di-halide having the formula R AlX wherein R is a hydrocarbon radi- 2) n Rs 2)n O N- -Rr wherein R is a radical selected from the group consisting of alkyl radicals containing 1 to 20 carbon atoms, phenyl, carboxyl, OR, -N(R) and 0 onn dNntna wherein R is an alkyl radical containing 1 to 4 carbon atoms, n is an integer of 1 to 4, and wherein each of R and R is a radical selected from the group consisting of hydrogen, alkyl radicals containing 1 to 8 carbon atoms, phenyl and cyclohexyl, R is a radical selected from the group consisting of alkyl radicals containing 1 to 4 carbon atoms and phenyl and n is an integer of l to 4, and wherein, R R and R are alkyl radicals containing 1 to 8 carbon atoms, x and y are who-1e numbers from 1 to 3 and 0 to 2, respectively, the sum of x and y being 3 and x and y are whole numbers from 1 to 2, the sum of x and y being 3, the molar ratio of transition metal compound to third component being within the range of 1:1 to 1:011.

2. In the polymerization of propylene to form solid crystalline polymer, the improvement which comprises effecting the polymerization in the presence of a catalytic mixture consisting essentially of a lower alkyl aluminum dihalide, a titanium halide [and a third component selected from the amides having the formula:

0 R2 R1(UJN/ wherein R is a radical selected from the group consisting of alkyl radicals containing 1 to 20 carbon atoms, phenyl, carboxyl, OR, --N(R) and wherein R is an alkyl radical containing 1 to 4 carbon atoms and wherein n is an integer of 1 to 4, and wherein each of R and R is a radical selected from the group consisting of hydrogen, alkyl radicals containing 1 to 8 carbon atoms, phenyl and cyclohexyl, the molar ratio of titanium halide to third component being within the range of 1:1 to 110.1.

3. In the polymerization of propylene to form solid crystalline polymer the improvement which comprises effecting the polymerization in the presence of a catalytic mixture consisting essentially of a lower alkyl aluminum dihalide, a titanium halide and a third component selected 1 0 from the amides having the formula P(NR R (OR wherein R R and R are alkyl radicals containing 1 to 8 carbon atoms, and x and y are whole numbers from 11 to 3 and 0 to 2, respectively, the sum of x and y being 3, the molar ratio of titanium halide to third component being within the range ofil :1 to 120.1.

4. In the polymerization of propylene to form solid crystalline polymer the improvement which comprises effecting the polymerization in the presence of a catalytic mixture consisting essentially of a lower alkyl aluminum dihalide, a titanium halide and a third component selected from the amides having the tormula:

wherein R R and R are alkyl radicals containing 1 to 8 carbon atoms, and x and y are whole numbers from 1 to 2, the sum of 2: and y being 3, the molar ratio of titanium halide to third component being within the range of 1:1 to 1: 0. 1.

15. In the polymerization of propylene to form solid crystalline polymer the improvement which comprises effecting the polymerization in liquid dispersion in an organic liquid and in the presence of a catalytic mixture consisting essentially of ethyl aluminum dichloride and titanium trichloride and a molar ratio of titanium trichloride and N,l I-dimethylformamide within the range of 1: 1 to 1:011.

6. The method according to claim 5 wherein vanadium trichloride is used in the catalyst mixture in place of titanium trichloride.

7. The method according to claim 5 wherein N,N-dimethylacetamide is used in the catalyst mixture in place of NlN-dimethylform amide.

8. In the polymerization of propylene to form solid crystalline polymer the improvement which comprises effecting the polymerization in liquid dispersion in an inert organic liquid and in the presence of a catalytic mixture consisting essentially of ethyl aluminum dichloride and titanium tetrachloride and a molar ratio of titanium tetrachloride to .N,N,N',N'-tetramethyladipam-ide within the range of 1:1 to 1:011.

9. 'In the polymerization of propylene to form solid crystalline polymer the improvement which comprises elfecting the polymerization in liquid dispersion in an inert liquid hydrocarbon vehicle and in the presence of a catalytic mixture consisting essentially of ethyl aluminum dichloride and titanium tetrachloride and a molar ratio of titanium tetrachloride and ethyl N,N-tetraethyl amidophosphate within the range of 1:1 to 120.1.

'10. As .a composition of matter, a catalytic mixture consisting essentially of :an aluminum dihalide having the formula R AlX wherein R is a hydrocarbon radical containing 1 to 12 carbon atoms and selected from the group consisting of alkyl, aryl and aralkyl, and the halogen atoms being selected from the group consisting of chlorine, bromine and iodine, -a compound of a transition metal selected from the group consisting of titanium, vanadium, zirconium, chromium and molybdenum, said compound being selected from the :group consisting of halides, alkoxyhalides .and acetylacetonates, and a third component selected from the amides having the formulas:

and

i (NR o) x,( 31) y;

wherein R is a nadical selected from the group consisting of alkyl radicals containing 1 to carbon atoms, phenyl, carboxyl, OR, -N (R) and it k uo oNmm wherein R is an alkyl radical containing 1 to 4 carbon atoms, n is an integer of 1 to 4, and wherein each of R and R is .a radical selected from the group consisting of hydrogen, alkyl madica-l's containing 1 to 8 carbon atoms, phenyl and cyclohexyl, R is a radical selected fnorn the group consisting of alkyl radicals containing 1 to 4 carbon atoms and phenyl and n is an integer of 1 to 4, and wherein R R and R are alkyl radicals containing =1 to 8 carbon atoms, x and y are Whole numbers from '1 to 3 and 0 to 2, respectively, the sum of x and y being 3 and x and y are whole numbers from 1 to 2, the sum of x and y being 3, the molar ratio of transition metal compound to third component being within the range of lll iO-lZOll.

11. As a composition of matter, a catalytic mixture consisting essentially of a lower alkyl aluminum dihalide, a titanium halide and a third component selected from the amides having the formula:

wherein R is a radical selected from the group consisting of alkyl radicals containing 1 to 20 carbon atoms,

phenyl, carboxyl, OR, N(R) and i (CHg) CNRgR3 wherein R is an alkyl radical containing 1 to 4 carbon atoms and wherein n is an integer of 1 to 4, and wherein each of R and R is a radical selected from the group consisting of hydrogen, alkyl radicals containing 1 to 8 carbon atoms, phenyl and cyclohexyl, the molar ratio of titanium halide to third component being within the range of1:1to1:0.1.

12. As a composition of matter, a catalytic mixture consisting essentially of a lower alkyl aluminum dihalide, a titanium halide and a third component selected from the amides having the formula P(NR R ),,(OR wherein R R and R are alkyl radicals containing 1 to 8 carbon atoms, and x and y are whole numbers from 1 to 3 and 0 to 2, respectively, the sum of x and y being 3, the molar ratio of titanium halide to third component being within the range of 1:1 to 1:0.1.

13. As a composition of matter, a catalytic mixture consisting essentially of :a lower alkyl aluminum dihalide, a titanium halide and a third component selected from the amides having the formula:

wherein R R and R are alkyl radicals containing 1 to 8 carbon atoms and x and y are whole numbers from 1 to 2, the sum of x and y being 3, the molar ratio of titanium halide to third component being within the range of 1:1 to 1:0.1.

14. As a composition of matter, a catalytic mixture consisting essentially of ethyl aluminum dichloride and titanium trichloride and a molar ratio of titanium tri chloride and N,N-dimethylformamide within the range of 1:1 to 1:0.1.

15. A composition according to claim 14 wherein vanadium trichloride is used in the catalyst mixture in place of titanium trichloride.

16. A composition according to claim 14 wherein N,N,- dimethylacetamide is used in the catalyst mixture in place of N,N-dimethylformamide.

17. As a composition of matter, a catalytic mixture consisting essentially of ethyl aluminum dichloride and titanium tetrachloride and a molar ratio of titanium tetrachloride to N,N,N',N'-tetramethyladipamide within the range of 1:1 to 1:0.1.

18. As a composition of matter, a catalytic mixture consisting essentially of ethyl aluminum dichloride and titanium tetrachloride and a molar ratio of titanium tetrachloride and ethyl N,N-tetraethyl amidophosphate within the range oflzlto 1:0.1.

References Cited by the Examiner UNITED STATES PATENTS 2,886,561 5/59 Reynolds et a1 260-93] 2,965,627 12/60 Field et a1 260-937 2,969,345 1/61 Cooveret al. 26094.9 3,004,020 10/61 Young et al. 26094.9

JOSEPH L. SCHOFER, Primary Examiner.

LESLIE H. GASTON, WILLIAM H. SHORT,

Examiners. 

1. IN THE POLYMERIZATION OF AN OLEFINIC HYDROCARBON MATERIAL CONTAINING AT LEAST THREE CARBON ATOMS TO FORM SOLID CRYSTALLINE POLYMER, THE IMPROVEMENT WHICH COMPRISES CATLYZING THE POLYMERIZATION WITH A CATALYTIC MIXTURE CONSISTING ESSENTIALLY OF AN ALUMINUM DIHALIDE HAVING THE FORMULA R1ALX2 WHEREIN R1 IS A HYDROCARBON RADICAL CONTAINING 1 TO 12 CARBON ATOMS AND SELECTED FROM THE GROUP CONSISTING OF ALKYL, ARYL AND ARALKYL, AND THE HALOGEN ATOMS BEING SELECTED FROM THE GROUP CONSISTING OF CHLORINE, BROMINE AND IODINE, A COMPOUND OF A TRANSITION METAL SELECTED FROM THE GROUP CONSISTING OF TITANIUM, VANADIUM, ZIRCONIUM, CHROMIUM AND MOLYBDENUM, SAID COMPOUND BEING SELECTED FROM THE GROUP CONSISTING OF HALIDES, ALKOXYHALIDES AND ACETYLACETONATES, AND A THIRD COMPONENT SELECTED FROM THE AMIDES HAVING THE FORMULAS: 